Stabilized ferromagnetic chromium dioxide and process for obtaining same

ABSTRACT

A ferromagnetic chromium dioxide stabilized by coating the particles thereof with a stabilizing substance is disclosed, wherein the stabilizing substance consists essentially of an equimolecular mixture of Fe 2  O 3  and MnO or of a mixture of ferrite MeFe 2  O 4  with oxides Fe 2  O 3  and MeO, wherein Me represents Cu, Co, Zn or Mg and wherein the molar ratio Fe 2  O 3  /MeO is equal to 1, the quantity of the ferrite in the mixture being such as results from calcining, at temperature between 250° and 350° C., equimolecular quantities of Fe 2  O 3  and MeO. A process for obtaining the stabilized CrO 2  is also disclosed wherein the CrO 2  is dispersed in water and on it are co-precipitated Fe(OH) 3  and Mn(OH) 2  or Me(OH) 2  in stoichiometric quantities with respect to each other; after which the CrO 2 , in admixture with the hydroxides, is separated from the water, dried at a temperature not exceeding 100° C. and then calcined at temperatures between 250° and 350° C.

The present invention relates to a stabilized ferromagnetic chromium dioxide and to a process for obtaining the same.

Chromium dioxide is a material of high magnetic characteristics that finds its main application in the field of magnetic tape recording. Chromium dioxide displays a certain chemical reactivity towards water and certain easily oxidizable functional groups, such as for instance hydroxyl or amine groups. These functional groups are often present in the resins used in the formulations for magnetic tapes, whereupon the CrO₂ particles incorporated in the tape may oxidize the functional groups, being themselves reduced, at least on the surface, to chromium compounds having a lower valency, such as CrOOH, which are not ferromagnetic as a result of which the residual magnetization of the tape may drop in the course of time. As a consequence, a tape on which there has been made a recording may present a drop in the output level after a period of time.

It is known to stabilize the CrO₂ by subjecting the surface of the particles thereof to a reducing treatment by making it react, for instance, with H₂ S or with alkaline bisulphites. Such a treatment, however, has the drawback of consuming via the reduction reaction a considerable quantity (up to about 30%) of the treated CrO₂.

It has also been suggested to stabilize the CrO₂ by coating the particles thereof with various substances that are insoluble in water, for instance SiO₂ or Al₂ O₃. It was not possible, however, to obtain an appreciable stabilizing effect with such coatings; while the CrO₂ particles dispersed in water showed after such a treatment a considerable reduction of their reactivity with water, no appreciable improvement could be detected when the stability of the CrO₂ was tested on the tapes themselves.

Thus, one object of this invention is that of providing a chromium dioxide that will show a high chemical stability towards water and oxidizable organic substances, thus displaying a high chemical stability in the magnetic tapes in which it is used.

Another object of this invention is that of achieving this result by means of a simple coating, thus avoiding the consumption of a part of the CrO₂ during the stabilizing treatment.

Still another object of the invention is that of providing a process for obtaining such a stabilized CrO₂.

All these and other useful objects are achieved by providing a ferromagnetic chromium dioxide stabilized by coating the particles thereof with a stabilizing substance which, according to this invention, consists or consists essentially of an equimolecular mixture of Fe₂ O₃ and MnO or a mixture of ferrite MeFe₂ O₄ with the oxides Fe₂ O₃ and MeO, wherein Me represents Cu, Co, Zn, or Mg, and wherein the molar ratio Fe₂ O₃ /MeO is equal to 1, the quantity of ferrite in the mixture being equal to that which is formed by calcining equimolecular quantities of Fe₂ O₃ and MeO at temperatures between 250° and 350° C.

The quantity of the stabilizing coating substance, in general, is between 2% and 12% by weight, referred to the CrO₂. Quantities lower than 2% may exert an insufficient stabilizing effect, while quantities greater than 12% do not in general improve the stability of the products. For the purpose of this invention, there are preferably used quantities of coating between 3% and 10% based on the weight of the CrO₂.

The mixtures based on Cu or Co ferrites and oxides and those based on Mn oxide in general confer upon the CrO₂ a greater stability in comparison with those based on Zn or Mg ferrites and oxides and they are, therefore, preferred. Particularly preferred are the mixtures based on Cu ferrite and oxide.

The CrO₂ stabilized with oxides or ferrites and oxides according to this invention may be obtained by means of a three-stage process wherein:

In the first stage, the CrO₂ is dispersed in water and on it are co-precipitated Fe(OH)₃ and Mn(OH)₂ or Me(OH)₂, taken in stoichiometric quantities with respect to each other. Thereupon the CrO₂ in admixture with the hydroxides is separated from the water. In the second stage, the mixture is dried at a temperature not exceeding about 100° C. In the third stage the dried product is calcined at a temperature which in general is between 250° and 350° C.

In the first stage, the co-precipitation of the hydroxides may be achieved by reacting hydrosoluble salts of the metals, e.g., chlorides or sulphates, with an aqueous solution of an alkaline hydroxide, for instance NaOH, or NH₃. The alkali or the ammonia is metered in such quantities as to bring the CrO₂ slurry containing the metal salts to pH values that are optimal for the co-precipitation, that is, to values in general between 8 and 10.

In the second stage, that is, during the drying, it is convenient to operate at a temperature not exceeding 100° C., because above this temperature the CrO₂ that is still in contact with the water may partially react therewith.

In the third stage, the formation of ferrite by reaction of Fe₂ O₃ with MeO takes place. This reaction is not complete whereupon the coating consists of a mixture of MeFe₂ O₄, Fe₂ O₃ and MeO. The quantity of ferrite that forms is so much the higher the higher the calcining temperature. There is no formation of ferrite in the case of Mn. In any case, one obtains a particularly adherent coating on the CrO₂ particles.

Calcining temperatures lower than about 250° C. usually do not insure a good stabilization of the CrO₂, while temperatures greater than about 350° C., in general, should be avoided because these may cause partial degradation of the CrO₂. Preferably one should operate between 300° and 350° C., while the best results are usually obtained between 330° and 350° C.

The coating thus consists of a calcined product obtained at between 250° and 350° C., but preferably at between 300° and 350° C., from equimolecular quantities of Fe₂ O₃ and MnO, CuO, CoO, ZnO or MgO.

While the quantity of ferrite formed increases with the increasing calcining temperature, this also depends on the nature of the metal Me. Thus, the coatings formed by calcining at 350° C. contain about 25% by weight of MeFe₂ O₄ (calculated on the total weight of the coating) in the case of Cu; about 35% in the case of Co; about 60% in the case of Zn; and about 75% in the case of Mg. These quantities are determined on the basis of diffractometric X-ray analysis.

The coating of CuFe₂ O₄, Fe₂ O₃ and CuO, formed by calcining at temperatures between 250° and 350° C., has a percentage weight of CuFe₂ O₄ generally between 11% and about 25%. The preferred coating, obtained by calcining at temperatures between 300° and 350° C., has a content in CuFe₂ O₄ generally between about 18% and about 25%.

Any type of ferromagnetic chromium dioxide may be used as starting CrO₂. There may be used a CrO₂ free of modifiers as well as a CrO₂ modified with any modifying element of CrO₂ such as for instance: Sb, Te, Fe, La and Ru or any combination of modifying elements such as for instance: Sb+Fe, Sb+Te, Te+Fe, La+Fe, Sb+Te+Fe, etc., etc.

The chromium dioxide modified with a modifying element, or with a combination of modifying elements, is described in numerous patents such as for instance in the following U.S. Pat. Nos. 2,885,365; 2,923,683; 2,923,684; 3,034,988; 3,068,176; 3,371,043; 3,640,871; 3,687,851; and 3,874,923.

The greatest benefit is obviously obtained when the starting CrO₂ has characteristics that make it well suited for use in magnetic tapes; that is, a coercive force H_(c) of at least 450 Oersted and a residual magnetization of at least 1500 Gauss, a mean particle length of not more than 0.5 microns, and an axial ratio (length/width ratio) of the particles of around 10.

The best stability, in general, is attained when the starting CrO₂ particles are suitably disaggregated so as to bring the mean size of the agglomerates to under 150 microns, and preferably under 50 microns. Best results are obtained in general when bringing this mean size down to below 10 microns.

The disaggregation of the particles may be carried out by either dry or wet grinding. Particularly convenient is wet grinding, for instance in a rotating jar containing a suitable grinding material, for instance steatite balls, or in a micro-ball mill with micro-balls made for instance of steel or ceramic material, or again in a vessel containing glass microspheres, subjected to shaking.

Wet grinding is usually carried out in water with a concentration in CrO₂ generally between 150 and 350 g per liter of slurry, but preferably between 250 and 300 g/lt.

The first stage of the treatment is usually conducted at temperatures between 20° and 100° C., but preferably between about 60° and 90° C.

The concentration of CrO₂ is usually between 50 and 100 grams per liter of slurry. It is advisable to operate under vigorous stirring in order to ensure a uniform distribution of the reactants and of the reaction products in the chromium dioxide mass.

The iron salt used for the purpose may be either ferric or ferrous. In this latter case, one first precipitates Fe(OH)₂ which is then oxidized to Fe(OH)₃ with an oxidizing agent. It is convenient to carry out the oxidation by bubbling a stream of air or oxygen through the reaction medium. The bubbling offers the advantage of providing an excellent mixing of the slurry and, thus, may also be used when starting from a ferric salt.

The iron salt and the salt of Mn or Me may be added separately on contemporaneously. When wet grinding the CrO₂, either one or both of the salts may be additioned to the CrO₂ slurry before the grinding itself.

The alkali or ammonia solution, on the contrary, is added as the last reactant. This addition may be carried out, for instance, in a period of time between 10 and 60 minutes, but preferably in about 30 minutes, until the desired pH value is reached.

Once the desired pH value has been attained, it is convenient to continue the stirring for a further period of time, e.g. for two hours, while keeping the temperature unaltered.

The slurry obtained at the end of the first stage is separated from the water, for instance by filtering, and is then washed in water to remove the soluble salts that were produced during the co-precipitation reaction.

The drying of the cake is carried out at temperatures not exceeding about 100° C. as already previously explained, for instance at temperatures between 60° and 90° C.

It is advisable to apply certain expedients for shortening the drying time; for this purpose the cake may be heated, for instance, under vacuum, or it may be imbibed with acetone before being heated. These two expedients may be used together.

The dried cake is then dry-ground, for instance in an impact stud mill with counter-rotating stud discs, and is then calcined at the temperatures indicated previously. The calcining is carried out, in general, for a period of at least 3 (three) hours, but preferably for a period of time between 5 hours and 10 hours.

The operation may be carried out either in a static oven or in a rotary furnace.

Since the co-precipitation yield amounts to 100%, the quantity of coating formed will coincide with the quantity of Fe₂ O₃ and bivalent metal oxide introduced into the first stage.

From the diffractometric X-ray examination, it is shown that the coating of the CrO₂ consists of oxides (in the case of Mn) or ferrite mixed with Fe₂ O₃ and MeO (in the case of Cu, Co, Zn and Mg).

The products according to this invention show a considerable stability with respect to water and to oxidizable organic substances and, thus, show a considerable stability in the magnetic tapes.

The stability of these products has been determined on a tape under particularly severe conditions according to a method per se known, which consists in exposing for a number of days a magnetic tape made with CrO₂ in a hot environment at a high relative humidity and in measuring the decay of the residual magnetization and of the saturation magnetization of the tape caused by such an exposure. Such a decay is substantially proportional to the decaying of the CrO₂.

The following examples are given in order still better to illustrate the inventive ideas underlying this invention.

EXAMPLE 1

The starting chromium dioxide was a CrO₂ modified with 650 ppm of Te and 1500 ppm of Fe. Its coercive force (measured in a field of 1000 Oersted) amounted to 550 Oersted; its maximum magnetization B_(m) (also measured in a field of 1000 Oersted) equaled 3015 Gauss; the residual magnetization B_(r) amounted to 1920 Gauss.

300 grams of this chromium dioxide were placed into a container provided with a tight lid, whose volume amounted to 4000 cc. Into the same container were also put 2700 g of glass spheres having a diameter of 2.5 mm and 1200 g of deionized water.

This container was then fixed on a Red Devil apparatus which exerted a vigorous shaking that will cause the milling of the chromium dioxide. At the end of the milling step the average or mean size of the agglomerates of particles proved to be lower than 10 microns. The glass spheres were then separated from the CrO₂ slurry by retaining them on a fine net and they were then washed with 4740 g of de-ionized water. The washing water was added to the slurry whereby the concentration in CrO₂ of the latter dropped to 50 g/lt.

6000 cc of this slurry were then placed into a 10 liter beaker, vigorously stirred with a blade stirrer, and then heated to 65° C.

To the heated slurry were then added 55.78 g of FeSO₄. 7H₂ O and 25.05 grams of CuSO₄.5H₂ O dissolved in 1000 ml of deionized water.

The dosing of the metal ions was such as to obtain, after calcining, 8 g of coating per 100 g of CrO₂.

After about 30 minutes there was added some NaOH solution having a concentration of 70 g/lt so as to attain in a further 30 minutes a pH value of 9.5. The temperature was then maintained at 65° C. for about 2 hours while maintaining the stirring and at the same time bubbling air drawn from a bottle in the quantity of 30 normal liters per hour.

The CrO₂ slurry was thereupon filtered under vacuum on a Buchner funnel and then washed up to the elimination of the SO₄ ⁻⁻ ions from the washing waters.

In a second stage the cake was dried in an oven under a vacuum of 20 mmHg at 90° C. for 12 hours. The dry CrO₂ was thereupon dis-aggregated by means of dry milling in an Alpine impact stud mill with counter-rotating stud discs.

The powdery product was finally calcined in a third stage, in a rotary furnace, at a temperature of 350° C., for 10 hours.

The stabilized product thus obtained displayed a coercive force of 545 Oersted a maximum magnetization of 2600 Gauss and a residual magnetization of 1600 Gauss.

Upon diffractometric X-ray analysis, the coating appeared to consist of CuFe₂ O₄, alpha-Fe₂ O₃ and CuO. The proportion of CuFe₂ O₄ amounted to about 25% by weight of the coating.

For the evaluation of the stability of the product, there was prepared a film according to the following procedure:

To 5 g of stabilized chromium dioxide were added 15 g of a varnish formulation for CrO₂ consisting of:

    ______________________________________                                         polymeric compounds (saturated                                                 polyurethane and vinyl acetate                                                 and vinyl chloride copolymer)                                                                         18% by weight                                           methylethylketone      40% by weight                                           tetrahydrofuran        20% by weight                                           dimethylacetamide      20% by weight                                           anionic surfactant (conventional)                                                                      2% by weight                                           ______________________________________                                    

To this mixture were then added 15 g of tetrahydrofuran and the whole was introduced into a 100 ml glass container together with 45 g of small glass spheres of 5 mm diameter.

This container was then placed in a Red Devil vibration disperser where it was subjected to vigorous stirring for one hour. After this time there were added a further 10 g of the formulation and 5 g of tetrahydrofuran and stirring went on for another 5 minutes.

The homogeneous varnish thus obtained was spread on a flexible support consisting of a plasticized cardboard giving to the film spreader a thickness of 8 mils (203 microns).

The spread varnish, allowed to dry for 24 hours, was then measured for B_(m) and B_(r) values by means of an alternating current hysteresigraph with a magnetizing field of 1000 Oe. The cardboard supported film was then exposed for 4 days at 65° C. in an environment having a relative humidity of 50%.

Then B_(m) and B_(r) were measured again and the percentage decrease of these values due to the exposure was evaluated. The drop in B_(m) and B_(r) proved equal to 12%.

With an identical film prepared according to the same procedures, starting from 5 g of the same CrO₂ not stabilized but subjected to the same stability test, the loss in B_(m) and B_(r) was equal to 23%.

EXAMPLES 2-5

The starting chromium dioxide contained 700 parts per million of Te and 1500 ppm of Fe. This chromium dioxide showed the following magnetic properties: H_(c) =590 Oersted; B_(m) =2900 Gauss; B_(r) =1800 Gauss.

It was subjected to the same procedures as those indicated in Example 1, except that there were used different quantities of reactants in order to coat the product with different quantities of stabilizing agent.

The stability on a magnetic film was evaluated following the same procedures as those indicated in Example 1. The characteristics of the stabilized product and the results of the stability tests are recorded in Table 1.

For comparative purposes, there are also reported the results of stability tests carried out on a sample of the same CrO₂ but not stabilized.

EXAMPLES 6-9

Here the procedure was as in previous Examples 2 to 5, except that the calcining temperature was 300° C. The characteristics of the products thus obtained and the results of the stability tests on them are recorded on Table II.

Under X-ray diffractometric analysis, the coating of Example 9 was shown to be composed of CuFe₂ O₄, alpha-Fe₂ O₃ and CuO. The proportion of CuFe₂ O₄ amounted to about 18% by weight of the coating.

                                      TABLE I                                      __________________________________________________________________________                      Magnetic Properties of the                                    Quantity of coating:                                                                            Stabilized CrO.sub.2                                                                           Stability Test on                             Example                                                                             % by weight with re-                                                                       H.sub.c                                                                              B.sub.m                                                                             B.sub.r                                                                             the film: drop of                             No.  spect to the CrO.sub.2                                                                     in Oersted                                                                           in Gauss                                                                            in Gauss                                                                            B.sub.m in percentage                         __________________________________________________________________________     2    2.5         590   2750 1700 15                                            3    5           590   2650 1650 13                                            4    7.5         585   2565 1615 12.5                                          5    10          595   2450 1500 12                                            Comparative test with the same CrO.sub.2 not stabilized                                                         23                                            __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________                      Magnetic Properties of the                                    Quantity of coating:                                                                            Stabilized CrO.sub.2                                                                           Stability Test on                             Example                                                                             % by weight with re-                                                                       H.sub.c                                                                              B.sub.m                                                                             R.sub.r                                                                             the film: drop of                             No.  spect to the CrO.sub.2                                                                     in Oersted                                                                           in Gauss                                                                            in Gauss                                                                            B.sub.m in percentage                         __________________________________________________________________________     6    2.5         595   2680 1680 17.5                                          7    5           590   2600 1620 17                                            8    7.5         595   2550 1600 17                                            9    10          595   2300 1450 16.5                                          Comparative test with the same CrO.sub.2 not stabilized                                                         23                                            __________________________________________________________________________

EXAMPLE 10

The starting chromium dioxide was modified with 1200 ppm of Te and 1500 ppm of Fe and showed the following magnetic properties: H_(c) =620 Oersted; B_(m) =2800 Gauss; B_(r) =1750 Gauss.

It was worked up as in Example 1, except that the quantities of reactants were such as to give a 6% by weight coating.

The magnetic characteristics of the stabilized product were the following: H_(c) =605 Oersted; B_(m) =2600 Gauss; B_(r) =1600 Gauss.

The drop in B_(m), in the measuring of the stability, was equal to 13% against a value of 27% for the starting product.

EXAMPLE 11

Example 10 was repeated, except that in this case there was used Fe₂ (SO₄)₃.4H₂ O instead of FeSO₄.7H₂ O. Air was also bubbled through as in the other examples.

In the stability test, the drop in B_(m) proved to be 13% against a value of 27% for the non-stabilized product.

EXAMPLES 12-13

The starting CrO₂ was modified with 1000 ppm of Te and 1500 ppm of Fe and showed the following magnetic properties: H_(c) =600 Oersted; B_(m) =2850 Gauss; B_(r) =1700 Gauss.

It was worked up as in Example 1, except that the first stage was carried out at 20° C. (Example 12) or at 80° C. (Example 13) instead of at 65° C.

In Example 12 the stabilized product showed the following magnetic properties: H_(c) =595 Oersted; B_(m) =2620 Gauss; B_(r) =1550 Gauss, and the drop of B_(m) in the tape amounted to 16% against 30% for the non-stabilized product.

In Example 13 the stabilized product showed the same magnetic properties as those of Example 12, while the drop in B_(m) in the tape amounted to 12%.

EXAMPLES 14-17

In these examples Mn, Mg, Co and Zn compounds were used instead of Cu compounds.

The CrO₂ of Example 12 was employed and the procedures of Example 1 were followed, except that the quantity of coating amounted to 10%, and the starting bivalent metal salt was respectively MnSO₄.H₂ O; MgSO₄.7H₂ O; CoSO₄.7H₂ O; and ZnSO₄.7H₂ O.

The characteristics of the stabilized products and the results of the stability tests are recorded in Table III.

The coating of the product of Example 14 consists of MnO and Fe₂ O₃ and is free of ferrite.

The coating of the product of Example 15 consists of MgFe₂ O₄ (about 75% by weight), MgO and alpha-Fe₂ O₃.

The coating of the product of Example 17 consists of ZnFe₂ O₄ (about 60% by weight), ZnO and alpha-Fe₂ O₃.

                                      TABLE III                                    __________________________________________________________________________                              Magnetic Properties of the                                                                     Test of Stability                                  Quantity of coating:                                                                       Stabilized CrO.sub.2                                                                           in the film: drop                     Example                                                                             Nature of the                                                                          % by weight with re-                                                                       H.sub.c                                                                              B.sub.m                                                                             B.sub.r                                                                             of B.sub.m in per-                    No.  Bivalent Metal                                                                         spect to the CrO.sub.2                                                                     in Oersted                                                                           in Gauss                                                                            in Gauss                                                                            centage                               __________________________________________________________________________     14   Mn      10          600   2600 1500 14                                    15   Mg      10          605   2550 1450 22                                    16   Co      10          595   2580 1500 15.5                                  17   Zn      10          595   2600 1500 19.5                                  Comparative test with the same CrO.sub.2 not stabilized                                                                 30                                    __________________________________________________________________________

EXAMPLE 18

Here the procedure was as in Example 16, except that the first stage was carried out at 80° C. instead of at 65° C.

The stabilized product showed the following magnetic properties: H_(c) =585 Oersted; B_(m) =2600 Gauss; and B_(r) =1510 Gauss.

The drop of B_(m) in the tape amounted to 14% as against 25% for the non-stabilized product.

The coating consisted of CoFe₂ O₄ (about 35% by weight), CoO and alpha-Fe₂ O₃. 

What is claimed is:
 1. A ferromagnetic chromium dioxide stabilized by coating the particles thereof with a stabilizing substance, characterized in that the stabilizing substance consists essentially of a mixture of ferrite MeFe₂ O₄ with alpha-Fe₂ O₃ and MeO, wherein Me represents Cu, Co, Zn or Mg and where the molar ratio Fe₂ O₃ /MeO is equal to 1, said substance being present in an amount between 2 and 12% by weight based on the CrO₂ and having been formed in situ by precipitating onto the surface of the CrO₂ particles quantities of Fe(OH)₃ that are equivalent to a molar ratio Fe₂ O₃ /MeO of 1 and Me(OH)₂, drying the chromium dioxide coated with the hydroxides and calcining it at a temperature between 250° and 350° C., the quantity of the ferrite in the substance being that which is formed at said calcination temperature.
 2. A chromium dioxide according to claim 1, characterized in that Me is either Cu or Co.
 3. A process for obtaining CrO₂ stabilized according to claim 1, characterized in that the CrO₂ is dispersed in water and that on it are coprecipitated quantities of Fe(OH)₃ and Me(OH)₂ that are equivalent to a molar ratio Fe₂ O₃ /MeO of 1 and in that the CrO₂, containing the coprecipitated hydroxides, is separated from the water, dried at a temperature not exceeding 100° C. and calcined at temperatures between 250° and 350° C.
 4. A process according to claim 3, characterized in that Fe(OH)₃ and Me(OH)₂ are co-precipitated by reaction of water-soluble Me and ferric or ferrous iron salts with an aqueous solution of an alkaline hydroxide or of ammonia and that, in the case of a ferrous salt, first there is precipitated Fe(OH)₂ and this is then oxidized to Fe(OH)₃ by means of an oxidizing agent.
 5. A process according to claim 4, characterized in that the oxidation of Fe(OH)₂ is carried out by bubbling air or oxygen through the reaction medium.
 6. A process according to any one of claims 3 to 5, characterized in that the calcining is carried out at temperatures between 300° and 350° C. 